The present invention relates to a copolymer of vinyl or vinylidene monomers and a high reactivity polyolefin which is produced by free radical polymerization. The copolymers are useful in many applications, including coatings and adhesives and exhibit improved water resistance, impact strength, flexibility, and processability in many applications.
Blends of two or more polymers have often been made, for example in attempts to combine desirable properties of the individual polymers into the blend, to seek unique properties in the blend, or to produce less costly polymer products by including less expensive or scrap polymers in the blend. Compatible polymers tend to form blends that contain small domains of the individual polymers; in the case of xe2x80x9cmisciblexe2x80x9d polymers these occur at the molecular scale, resulting in properties usually considered characteristic of a single polymer. These may include the occurrence of a single glass-transition temperature and optical clarity. Compatible polymers that are not strictly miscible are still likely to form blends with properties that approach those of the miscible blends. Such properties as tensile strength, which rely upon adhesion of the domains to one another, tend not to be degraded when compatible polymers are blended.
Many polymers are poorly compatible with one another, and poor compatibility cannot necessarily be predicted accurately for a given polymer combination, but in general it may be expected when non-polar polymers are blended with more polar polymers. Poor compatibility in a blend can be determined by those skilled in the art, and often evidences itself in poor tensile strength or other physical properties, especially when compared to the component polymers of the blend. Microscopic evidence of poor compatibility may also be present, in the form of large, poorly adhered domains of one or more polymer components in a matrix of another polymer component of the blend. More than one glass-transition temperature may be observed, and a blend of otherwise transparent polymers may be opaque because the domain sizes are large enough to scatter visible light.
Much research has been directed toward finding ways to increase the compatibility of poorly compatible polymers when blended. Approaches that have been used include adding to the blend polymers which show incompatibility with the other, mutually compatible polymers; such added polymers act as a bridge or interface between the incompatible components, and often decrease domain size. Chlorinated polyethylene has been used as such an additive polymer, especially in blends of polyolefins with other, poorly compatible polymers.
Graft polymers, as of incompatible polymers A onto B, are known to aid in blending polymers A and B. Such graft polymers may also serve to aid in blending other incompatible polymers C and D, where A and C are compatible and B and D are compatible. Grafting of monomers capable of vinyl polymerization, such as, methyl methacrylate, styrene and the like, onto polyolefins has been attempted by many means. Grafting onto solid polymer by vapor-phase polymerization, by reaction in an extruder, by peroxidation of the olefinic backbone, and grafting onto pendant double bonds are all routes which have been attempted.
For example, U.S. Pat. Nos. 5,128,410 and 5,229,456 disclose a polymerized olefin having grafted thereto, by covalent bonding, a polymeric methacrylate chain of relatively high molecular weight. The methacrylate chain has a weight average molecular weight (Mw) of at least 20,000 and advantageously between about 30,000 and 150,000. The resulting polyolefin copolymer has a weight average molecular weight between about 50,000 and 1,000,000, preferably a weight average molecular weight of about 200,000-800,000. In the method of manufacturing the grafted copolymer, a non-polar polyolefin, preferably polypropylene or polyethylene, is introduced into an inert hydrocarbon solvent which dissolves (or swells) the polyolefin, by heating to a temperature at which the polyolefin is dissolved. While agitating the solution, methyl methacrylate (MMA) monomer, together with an initiator which generates a constant, low radical flux concentration sufficient to initiate polymerization of the monomer at the temperature of the solution and promote the formation of the covalent bond, is gradually added. The polyolefin with a side-chain grafted thereto is thereafter separated from the solvent by volatilizing the solvent, preferably in a devolatilizing extruder. The graft polymer is then blended with a suitable polyolefin such as polypropylene or polyethylene, and extruded into a desired shape.
U.S. Pat. No. 5,112,507 generically discloses compositions which comprise copolymers of an unsaturated acidic reactant and high molecular weight olefin wherein at least about 20 percent of the total high molecular weight olefin comprises the alkylvinylidene isomer, said copolymers having alternating succinic and polyalkyl groups. The only unsaturated acidic reactant exemplified is maleic acid. The high molecular weight olefin has a sufficient number of carbon atoms such that the resulting copolymer is soluble in lubricating oil. Suitable olefins include those having about 32 carbon atoms or more (preferably having about 52 carbon atoms or more). Preferred high molecular weight olefins include polyisobutenes. Especially preferred are polyisobutenes having number average molecular weights of from about 500 to about 5000 and in which the alkylvinylidene isomer comprises at least 50 percent of the total olefin. The copolymers are disclosed to be useful as dispersants in lubricating oils and fuels.
D.E. 4,030,399 discloses that polymers and copolymers of propylene which, to some extent, have vinylidene terminal groups can be functionalized to give polymers and copolymers of propylene with 0 to 40 wt % of other C2 and C8 1 -alkenes, having number average molecular weights (Mn) of 100 to 100,000, a Mw/Mn of 1 to 3, and one functional chain end per macromolecule where xe2x80x9cfunctionalityxe2x80x9d means a group containing a heteroatom which is bonded to a C atom. Polypropylene homopolymer is the only polymer exemplified. The functionalized polymers can be reacted with polar polymers to give copolymers of propylene.
Published European Patent Application No. 95110985.9 discloses conversion products of polyolefins with predominantly terminal double bonds and a numerical mean number average molecular weight of 250 to 10,000, which have an aliphatic hydrocarbon skeleton which is straight chain or carries C1-C4 alkyl side chains, with 1 to 10 mol per equivalent of double bond of one or more vinyl esters obtainable by reacting the disclosed polyolefins with the vinyl esters in the presence of a free radical initiator at temperatures of 40 to 220xc2x0 C., whereby these reaction products are then hydrolyzed to the corresponding alcohol or can be converted to the corresponding amines by reductive amination. The conversion products are used in fuel and lubricant compositions as additives.
U.S. Pat. No. 4,062,908 discloses the preparation of vinyl ester copolymers; more particularly, a free-radical induced bulk copolymerization of ethylenically unsaturated compounds is described. The use of the resulting copolymers for coating applications, particularly in non-aqueous dispersions, is also described. The patent discloses a process for the preparation of copolymers of monoethylenically unsaturated compounds in the presence of a free-radical forming initiator by bulk copolymerization as follows: A. 1-50 parts by weight of vinyl esters of saturated aliphatic monocarboxylic acids in which the carboxyl group is attached to a tertiary or quaternary carbon atom, and which carboxylic acids have at least 9 carbon atoms per molecule; B. 1-60 parts by weight of a vinyl aromatic hydrocarbon; C. 0-50 parts by weight of an ester, amide, and/or nitrite of an ethylenically unsaturated monocarboxylic acid having 3 to 4 carbon atoms per molecule; D. 0-30 parts by weight of an ester of an ethylenically unsaturated dicarboxylic acid having 4-5 carbon atoms per molecule; E. 0-20 parts by weight of an ethylenically unsaturated mono- or dicarboxylic acid, or anhydride thereof, having 3-5 carbon atoms per molecule, and F. 1-20 parts by weight of a monoethylenically unsaturated polymeric hydrocarbon having a molecular weight higher than 1000; with the total amount of ethylenically unsaturated monomers being 100 parts by weight. The process is characterized in that a reactor charge containing component (F) and, optionally part of the initiator, is heated to at least 150xc2x0 C., whereupon the other monoethylenically unsaturated components and initiator are gradually added during a period of from about 3 to 24 hours at a reaction temperature between 150xc2x0 C. and 200xc2x0 C. in one or more stages.
The present invention is a copolymer of at least one vinyl monomer and at least one high vinylidene polyolefin having a terminal vinylidene content of at least about 40%, preferably at least about 50% and more preferably at least about 60% and a number average molecular weight of about 200 to about 10,000, preferably about 300 to about 7,500, more preferably about 500 to about 5,000, most preferably about 500 to about 3,000. Copolymers of the present invention and produced by the method of the present invention generally have number average molecular weights of from about 80,000 to about 1,500,000 preferably about 300,000 to about 1,000,000. The aforesaid vinyl monomer is a compound of the formula CH2xe2x95x90C(R)X where R is hydrogen or C1-C6 alkyl and X is halogen; phenyl; or phenyl substituted with C1-C4 alkyl; xe2x80x94COOR1 where R1 is hydrogen or C1-C12 alkyl; xe2x80x94Cxe2x89xa1N; xe2x80x94C(O)NR2R3 where R2 and R3 are hydrogen or C1-C4 alkyl and may be the same or different; xe2x80x94(CH2)nCOOR1 where R1 is hydrogen or C1-C12 alkyl and n is an integer of from 1 to 4; or xe2x80x94CHxe2x95x90CHZ where Z is hydrogen or C1-C8 alkyl; or where both R and X are halogen. Preferably the aforesaid vinyl monomer is a compound of the formula: CH2xe2x95x90CHX where X is chlorine, phenyl, or phenyl substituted with C1-C4 alkyl; CH2xe2x95x90C(R)COOR1 where R is hydrogen or C1-C4 alkyl and R1 is hydrogen or C1-C10 alkyl; CH2xe2x95x90CHCxe2x89xa1N; CH2xe2x95x90CHC(O)NR2R3 where R2 and R3 are hydrogen or C1-C4 alkyl and may be the same or different; CH2xe2x95x90C(R)(CH2)nCOOR1 where R is hydrogen or C1-C4 alkyl, R1 is hydrogen or C1-C10 alkyl and n is an integer of from 1 to 4; or CH2xe2x95x90CHxe2x80x94CHxe2x95x90CHZ where Z is hydrogen or C1-C4 alkyl. More preferably, the aforesaid vinyl monomer is methacrylic acid, methyl methacrylate, butyl acrylate, butadiene, 2-ethylhexyl acrylate, styrene or vinyl chloride. Preferably the aforesaid high reactivity polyolefin is polyisobutylene.
A copolymer of the present invention is prepared in the method of the present invention by reacting at least one aforesaid high reactivity polyolefin and at least one aforesaid vinyl monomer reactant in the presence of a free radical initiator under polymerization conditions.
The present invention also includes compositions containing a copolymer of the present invention and useful in coating, adhesive, paint, structural, film, sheet pipe, toy, house siding, asphalt, thermoplastic and elastomer applications. The present invention also includes a coating composition containing a copolymer of the present invention. The present invention is also a multilayer structure comprising at least one substrate coated with at least one layer of a coating comprising a copolymer of the present invention. The substrate may be any material capable of being coated with a copolymer of the invention or a coating composition containing a copolymer of the invention. Such substrates may include, but are not limited to metal, wood, concrete, plastic, paper, textiles, polymers, glass, fiberboard, composites, fibers porcelain, polymers films and sheets, and the like.
The present invention relates to a copolymer of at least one high reactivity polyolefin having a terminal vinylidene content of at least about 40% and a number average molecular weight of about 200 to about 10,000 and at least one vinyl monomer of the formula CH2xe2x95x90C(R)X where R is hydrogen or C1-C6 alkyl and X is halogen, phenyl, phenyl substituted with C1-C4 alkyl, xe2x80x94COOR1 where R1 is hydrogen or C1-C12 alkyl, xe2x80x94Cxe2x89xa1N, xe2x80x94C(O)NR2R3 where R2 and R3 are hydrogen or C1-C4 alkyl and may be the same or different, xe2x80x94(CH2)nCOOR1 where R1 is hydrogen or C1-C12 alkyl and n is an integer of from 1 to 4, or xe2x80x94CHxe2x95x90CHZ where Z is hydrogen or C1-C8 alkyl; or where both R and X are halogen (in which case the aforesaid vinyl monomer is a vinylidene monomer such as vinylidene chloride or vinylidene fluoride).
In one preferred embodiment, the aforesaid at least one vinyl monomer is a compound of the formula:
(a) CH2xe2x95x90C(R)X where R is hydrogen or C1-C4 alkyl and X is phenyl or phenyl substituted with C1-C4 alkyl;
(b) CH2xe2x95x90C(R)COOR1 where R is hydrogen or C1-C4 alkyl and R1 is hydrogen or C1-C10 alkyl;
(c) CH2xe2x95x90CHCxe2x89xa1N;
(d) CH2xe2x95x90CHC(O)NR2R3 where R2 and R3 are hydrogen or C1-C4 alkyl and may be the same or different;
(e) CH2xe2x95x90CHR4 where R4 is halogen, preferably chlorine;
(f) CH2xe2x95x90C(R)(CH2)nCOOR1 where R is hydrogen or C1-C4 alkyl, R1 is hydrogen or C1-C10 alkyl and n is an integer of 1 to 4; or
(g) CH2xe2x95x90CY2 where Y is fluorine or chlorine;
In another preferred embodiment, the aforesaid at least one vinyl monomer is at least one compound of the formula:
(a) CH2xe2x95x90CHX where X is chlorine, phenyl, or phenyl substituted with C1-C4 alkyl;
(b) CH2xe2x95x90C(R)COOR1 where R is hydrogen or C1-C4 alkyl and R1 is hydrogen or C1-C10 alkyl;
(c) CH2xe2x95x90CHCxe2x89xa1N;
(d) CH2xe2x95x90CHC(O)NR2R3 where R2 and R3 are hydrogen or C1-C4 alkyl and may be the same or different; or
(e) CH2xe2x95x90CHxe2x80x94CHxe2x95x90CHZ where Z is hydrogen or C1-C4 alkyl.
In a more preferred embodiment, the aforesaid at least one vinyl monomer is an acrylic acid; an acrylate, such as butyl acrylate or 2-ethylhexyl acrylate; an alkylacrylic acid, such as methacrylic acid; an alkylacrylate, such as methyl methacrylate; a vinyl acid such as vinyl acetic acid; a vinyl nitrile, such as acrylonitrile, styrene, or a styrene derivative; a vinyl halide, such as vinyl chloride, vinyl bromide or vinyl fluoride; or a diene, such as butadiene. Thus, included in the present invention are copolymers of an aforesaid high reactivity polyolefin and one or more vinyl compounds selected from the group consisting of methacrylic acid, methyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, styrene, butadiene, acrylonitrile, vinyl chloride, and vinylidene chloride.
As employed herein, the term xe2x80x9cvinyl monomerxe2x80x9d includes vinylidene monomers. The term xe2x80x9cvinylidene monomerxe2x80x9d refers to compounds of the formula CH2xe2x95x90CY2 where Y is halogen, preferably fluorine or chlorine. Many vinyl and vinylidene monomers that are suitable for use in the present invention include, but are not limited to, those described in Billmeyer, Fred, W., TEXTBOOK OF POLYMER SCIENCE, 3rd Edition, John Wiley and Sons (1984) incorporated herein by reference in its entirety, and particularly those vinyl and vinylidene monomers discussed in Chapters 13 and 14 at pages 361-406 and include methacrylic acids and acrylates, for example C1-C12 acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate and 2-ethylhexyl acrylate; C1-C20 alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate and hexyl methacrylate; methacrylic acid, styrene (vinylbenzene), vinyl chloride, acrylonitrile, butadiene, vinylacrylonitrile butadiene styrene, acrylates, and styrene acrylonitrile.
High reactivity polyolefins suitable for use in the present invention generally are viscous, low molecular weight polyolefins having a high percentage of vinylidene olefinicityxe2x80x94that is, at least about 40%, preferably at least about 50%, more preferably at least about 60%, and most preferably at least about 80%, and a number average molecular weight of about 200 to about 10,000, preferably about 300 to about 7,500, more preferably about 500 to about 5,000, and most preferably about 500 to about 3,000. The aforesaid high reactivity polyolefins (also referred to as high vinylidene polyolefins or alkylvinylidene polyolefins) are preferably polymers or copolymers of C3-C20 olefins or copolymers of ethylene with a C3-C20 olefin.
As employed herein, the term xe2x80x9calkylvinylidenexe2x80x9d or xe2x80x9calkylvinylidene olefinxe2x80x9d refers to olefins and polyalkylene components having the following vinylidene structure 
wherein R5 is an alkyl or substituted alkyl group of sufficient chain length to give the resulting molecule an Mn of about 200 to about 10,000 and R6 is lower alkyl. Thus, R5 generally has at least about 10 carbon atoms, preferably at least about 50 carbon atoms and R6 is lower alkyl of about 1 to about 12 carbon atoms, preferably about 1 to about 6 carbon atoms, and more preferably methyl. Preferably, R5 has about 10 to about 750 carbon atoms, and more preferably R5 has about 20 to about 400 carbon atoms.
The aforesaid high reactivity polyolefins may be prepared according to the process described in Eaton, U.S. Pat. No. 5,068,490, which is incorporated herein by reference in its entirety. This process is especially useful for preparing high reactivity polyisobutylene. In the process disclosed therein, a 1-olefin containing feedstock is contacted with a BF3-tertiary etherate at xe2x88x92100xc2x0 C. to +50xc2x0 C. The tertiary ether can have the general formula: (I) 
where R1 is C1 to C20 hydrocarbyl or halo-substituted hydrocarbyl, and R2, R3 and R4 may be the same or different and are selected from the group consisting of (1) xe2x80x94CH2Rxe2x80x2 where Rxe2x80x2 is H, halogen, or C1 to C20 hydrocarbyl or halo-substituted C1 to C20 hydrocarbyl; (2) xe2x80x94CHxe2x95x90Rxe2x80x3 where Rxe2x80x3 is C1 to C20 hydrocarbyl or halo-substituted C1 to C20 hydrocarbyl; and (3) xe2x80x94Cxe2x89xa1Rxe2x80x2xe2x80x3 where Rxe2x80x2xe2x80x3 is C1-C20 hydrocarbyl or halo-substituted hydrocarbyl. Preferred tertiary ethers for use in preparation of the BF3-etherate complexes are those in which and R2, R3 and R4 in the above formula are methyl, and R1 is C1 to C10 hydrocarbyl. Particularly preferred are the alkyl tert-butyl ethers, for example, methyl t-butyl ether, n-butyl t-butyl ether; isopropyl t-butyl ether, di-tert-butyl ether, ethyl tert-butyl ether; pentyl tert-butyl ether; 1,1xe2x80x2-dimethylbutyl methylether, etc.
The aforesaid high reactivity polyolefins, (also referred to as high vinylidene polyolefins or alkylvinylidene polyolefins) are preferably polymers and copolymers of C3-C20 olefins or copolymers of ethylene with a C3-C20 olefin.
The aforesaid high reactivity polyolefins which can be used to prepare the copolymers of the present invention also include reactive, low molecular weight, viscous, essentially 1-olefin-containing poly(1-olefins) and copoly(1-olefins) that can be prepared employing a catalyst comprising a Periodic Group IVb metallocene and an aluminoxane and/or boron containing cocatalyst from a feedstock containing one or more C3 to C20 1-olefins. Such reactive, low molecular weight, viscous, essentially 1-olefin-containing poly(1-olefins) and copoly(1-olefins) and their method of preparation are described in Bagheri et al., U.S. Pat. No. 5,688,887, issued Nov. 18, 1997, and WO 93/24539, each of which is incorporated herein by reference in its entirety. Suitable essentially terminally-unsaturated, viscous, essentially-1-olefin-containing poly(1-olefins) or copoly(1-olefins) may be made by a process which comprises polymerizing under fluid phase conditions, preferably liquid phase conditions, a feedstock comprising more than 1 weight percent of at least one volatile hydrocarbon liquid and less than 99 weight percent based on total feedstock of one or more C3 to C20-olefins using a catalyst system comprising a titanium(IV), zirconium(IV), or hafnium(IV) metallocene and an aluminoxane cocatalyst to form a poly(1-olefin) or copoly(1-olefin) having a number average molecular weight in a range from about 300 to about 10,000, more preferably between about 300 and about 5000, and most preferably about 400 to about 3000, and terminal vinylidene content typically of more than 80%. Catalyst systems using a bis(cyclopentadienyl) or bis(indenyl) titanium(IV), zirconium(IV), or hafnium(IV) compound are preferred, particularly bis(cyclopentadienyl)-zirconium dichloride (CP2ZrCl2) or bis(indenyl) zirconium dichloride (In2ZrCl2). The resulting polymers are atactic. By essentially terminally-unsaturated is meant that preferably more than about 90%, more preferably more than about 95%, and most preferably more than about 99% of the polymer chains in the product polymer contain terminal unsaturation. The terminal unsaturation is preferably more than about 80%, more preferably more than about 90%, and most preferably more than about 95% of the vinylidene type. Such copolymers may also include copolymers of a 1-olefin and an alpha-omega diene. Such alpha-omega dienes may include, but are not limited to, 7-methyl-1,6-octadiene. These terminally unsaturated, viscous polymers are essentially poly(1-olefins) or copoly(1-olefins). By essentially poly(1-olefins) or copoly(1-olefins) is meant more than about a 95% and, more preferably, more than about a 98% 1-olefin content in the polymer chains except where, for example, an alpha-omega diene is added as described above.
Isobutene polymers that are suitable for use as the aforesaid high reactivity polyolefin in making the copolymers of the present invention also include those described in U.S. Pat. No. 4,152,499, incorporated herein by reference in its entirety, which are obtained by polymerizing isobutene with boron trifluoride as the initiator. Cocatalysts such as water or alcohols may be used in the polymerization.
High reactivity polyolefins suitable for use in preparing the copolymers of the present invention also include terminally unsaturated ethylene alpha-olefin polymers wherein the terminal unsaturation comprises ethenylidene (i.e., vinylidene) unsaturation as disclosed in U.S. Pat. No. 4,668,834, U.S. Pat. No. 5,225,092, U.S. Pat. No. 5,225,091, U.S. Pat. No. 5,229,022, U.S. Pat. No. 5,084,534, and U.S. Pat. No. 5,324,800, the disclosures of all of which are hereby incorporated by reference in their entirety. Such polymers are polymers of ethylene and at least one alpha-olefin having the formula H2Cxe2x95x90CHR, wherein R1 is a straight chain or branched chain alkyl radical comprising 1 to 18 carbon atoms and wherein the polymer contains a high degree of terminal ethenylidene unsaturation. Preferably R1 in the above formula is alkyl of from 1 to 8 carbon atoms, and more preferably is alkyl of from 1 to 2 carbon atoms. Such alpha-olefins include propylene, 1-butene, hexene-1, octene-1, 4-methylpentene-1, decene-1, dodecene-1, tridecene-1, tetradecene-1, hexadecene-1, heptadecene-1, octadecene-1, and mixtures thereof (e.g., mixtures of propylene and 1-butene, and the like). Exemplary of such polymers are ethylene-propylene copolymers, ethylene-butene-1 copolymers and the like. The molar ethylene content of the ethylene alpha-olefin polymers is preferably in the range of between about 20 and about 80 percent, and more preferably between about 30 and about 70 percent. When propylene and/or butene-1 are employed as comonomer(s) with ethylene, the ethylene content of such copolymers is most preferably between about 45 and about 65 percent, although higher or lower ethylene contents may be present.
The ethylene alpha-olefin polymers generally possess a number average molecular weight of from about 300 to about 10,000 (e.g. from 300 to 10,000) preferably from about 900 to 10,000; more preferably of from about 900 to 10,000 (e.g., from about 700 to about 10,000); from about 1500 to about 5,000. Such ethylene alpha-olefin polymers having a number average molecular weight within the range of from about 700 to about 5000 (e.g., 1500 to 3,000) are particularly useful in the present invention. Such polymers generally possess an intrinsic viscosity (as measured in tetralin at 135xc2x0 C.) of between about 0.025 and about 0.9 dl/g, preferably of between about 0.05 and about 0.5 dl/g, most preferably of between about 0.075 and about 0.4 dl/g. These polymers preferably exhibit a degree of crystallinity such that, when grafted, they are essentially amorphous. These ethylene alpha-olefin polymers are further characterized in that at least about 95% of the polymer chains possess terminal ethenylidene-type unsaturation. Thus, one end of such ethylene alpha-olefin polymers will be of the formula POLY-C(T1)xe2x95x90CH2 wherein T1 is C1 to C18, alkyl, preferably C1 to C8 alkyl, and more preferably C1 to C2 alkyl, (e.g., methyl or ethyl), and wherein POLY represents the polymer chain. The chain length of the T1 alkyl group will vary depending on the comonomer(s) selected for use in the polymerization. A minor amount of the ethylene alpha-olefin polymer chains can contain terminal ethenyl unsaturation, i.e., POLYxe2x80x94CHxe2x95x90CH2, and a portion of the polymers can contain internal monounsaturation, e.g. POLYxe2x80x94CHxe2x95x90CH(T1), wherein T1 is as defined above. The ethylene alpha-olefin polymers comprise polymer chains, at least about 40 percent of which possess terminal ethenylidene unsaturation. Preferably at least about 50 percent, more preferably at least about 60 percent, and most preferably at least about 75 percent (for example, 75-98%), of such polymer chains exhibit terminal ethenylidene unsaturation. The percentage of polymer chains exhibiting terminal ethenylidene unsaturation may be determined by FTIR spectroscopic analysis titration, or C13NMR.
The ethylene alpha-olefin polymers may be prepared as described in U.S. Pat. No. 4,668,834, U.S. Pat. No. 5,225,092, U.S. Pat. No. 5,225,091, U.S. Pat. No. 5,229,022, U.S. Pat. No. 5,324,800, U.S. Pat. No. 5,094,534, and European Patent Publications 128,045 and 129,368, the disclosures of all of which are hereby incorporated by reference in their entirety. The ethylene alpha-olefin polymers can be prepared by polymerizing monomer mixtures comprising ethylene in combination with other monomers such as alpha-olefins having from 3 to 20 carbon atoms (and preferably from 3 to 4 carbon atoms, that is, propylene, butene-1, and mixtures thereof) in the presence of a catalyst system comprising at least one metallocene (for example, a cyclopentadienyl-transition metal compound) and an alumoxane compound. The comonomer content of the ethylene alpha-olefin polymers can be controlled through the selection of the metallocene catalyst component and by controlling the partial pressure of the various monomers.
The catalysts employed in the production of the ethylene alpha-olefin polymers are organometallic coordination compounds which are cyclopentadienyl derivatives of a Group IVb metal of the Periodic Table of the Elements(56th Edition of Handbook of Chemistry and Physics, CRC Press[1975]) and include mono, di, and tricyclopentadienyls and their derivatives of the transition metals. Particularly desirable are the metallocene of a Group IVb metal such as titanium, zirconium, and hafnium. The alumoxanes employed in forming the reaction product with the metallocenes are themselves the reaction products of an aluminum trialkyl with water. In general, at least one metallocene compound is employed in the formation of the catalyst. Metallocene is a metal derivative of a cyclopentadiene. The metallocenes used to make the ethylene alpha-olefin polymers contain at least one cyclopentadiene ring. The metal is selected from the Group lVb, preferably titanium, zirconium, and hafnium, and most preferably hafnium and zirconium. The cyclopentadienyl ring can be unsubstituted or contain one or more substituents (e.g., from 1 to 5 substituents) such as, for example, a hydrocarbyl substituent (e.g., up to 5 C1 to C5 hydrocarbyl substituents) or other substituents, such as, for example, a trialkyl silyl substituent. The metallocene can contain one, two, or three cyclopentadienyl rings; however, two rings are preferred.
The alumoxane compounds useful in the polymerization process may be cyclic or linear. Cyclic alumoxanes may be represented by the general formula (Rxe2x80x94Alxe2x80x94O), while linear alumoxanes may be represented by the general formula R(Rxe2x80x94ALxe2x80x94O)nxe2x80x2AIR2. In the general formula R is a C1-C5 alkyl group such as, for example, methyl, ethyl, propyl, butyl, and pentyl, n is an integer of from 3 to 20, and nxe2x80x2 is an integer from 1 to about 20. Preferably, R is methyl and n and nxe2x80x2 are 4-18. Generally, in the preparation of alumoxanes from, for example, aluminum trimethyl and water, a mixture of the linear and cyclic compounds is obtained. Polymerization is generally conducted at temperatures ranging between about 20xc2x0 C. and about 300xc2x0 C., preferably between about 30xc2x0 C. and 200xc2x0 C. Reaction time is not critical and may vary from several hours or more to several minutes or less, depending upon factors such as reaction temperature, the monomers to be copolymerized, and the like. One of ordinary skill in the art may readily obtain the optimum reaction time for a given set of reaction parameters by routine experimentation. Polymerization pressures are preferably from about 10 to about 3,000 bar, and generally at a pressure within the range from about 40 bar to about 3,000 bar; and most preferably, the polymerization will be completed at a pressure within the range from about 50 bar to about 1,500 bar. The polymerization may be conducted employing liquid monomer, such as liquid propylene, or mixtures of liquid monomers (such as mixtures of liquid propylene and 1-butene), as the reaction medium. Alternatively, polymerization may be accomplished in the presence of a hydrocarbon inert to the polymerization such as butane, pentane, isopentane, hexane, isooctane, decane, toluene, xylene, and the like. In those situations wherein the molecular weight of the polymer product that would be produced at a given set of operating conditions is higher than desired, any of the techniques known in the prior art for control of molecular weight, such as the use of hydrogen and/or polymerization temperature control, may be used in the process for preparing the polymers.
The copolymers of the present invention are prepared in accordance with the method of the present invention by reacting an aforesaid highly reactive polyolefin with an aforesaid vinyl monomer in the presence of a free radical initiator and under polymerization conditions. Since the resulting copolymers of the present invention are generally mixtures, they will generally contain a mixture of individual molecules and polyalkyl groups of varying molecular weight. Also, mixtures of copolymer molecules having different degrees of polymerization will be produced. In general, the molecular weight of copolymers of the present invention ranges from about 80,000 to about 1,500,000, preferably from about 300,000 to about 1,000,000.
The preferred alkylvinylidene isomer of the aforesaid highly reactive polyolefin employed in the method of this invention comprises a methyl- or ethylvinylidene isomer, more preferably the methylvinylidene isomer. The especially preferred high reactivity polyolefins used to prepare the copolymers of the present invention are polyisobutenes which comprise at least about 60% of the more reactive methylvinylidene isomer, preferably at least about 80%, and more preferably at least about 95%. Suitable polyisobutenes include those prepared using BF3 catalysis. The preparation of such polyisobutenes in which the methylvinylidene isomer comprises a high percentage of the total composition is described in U.S. Pat. Nos. 4,152,499 and 4,605,808 incorporated herein by reference. By contrast, polyisobutenes and polyolefins produced by conventional AlCl3 catalysis, when reacted with the vinyl monomers used in the present invention in the presence of a free radical initiator, do not have sufficient terminal vinylidene content to produce copolymers having the improved properties associated with copolymers of the present invention and do not produce a copolymeric product.
For some vinyl monomers, the reaction may be conducted neat, that is, both the high reactivity polyolefin, and the vinyl monomer (or vinyl monomers) and the free radical initiator are combined in the proper ratio, and then stirred at the reaction temperature. Alternatively, the reaction may be conducted in a diluent. For example, the reactants may be combined in a solvent. Suitable solvents include those in which the reactants and free radical initiator are soluble or dispersible and include water, acetone, tetrahydrofuran, chloroform, methylene chloride, dichloroethane, toluene, dioxane, chlorobenzene, xylenes, or the like. After the reaction is complete, volatile components may be stripped off. When a diluent is employed, it is preferably inert to the reactants and products formed and is generally used in an amount sufficient to ensure efficient stirring.
In general, the copolymerization method of this invention can be initiated by any free radical initiator. Such initiators are well known in the art. However, the choice of free radical initiator may be influenced by the solvent or reaction temperature employed. The preferred free-radical initiators for copolymerization in emulsion or suspension polymerization are the persulfate-type polymerization initiators. Preferred persulfates include ammonium persulfate, sodium persulfate, potassium persulfate, and lithium persulfate. Ammonium persulfate is particularly preferred. Other free-radical initiators which can be used are the peroxide-type polymerization initiators and the azo-type polymerization initiators. Radiation can also be used as the initiator to initiate the reaction, if desired.
The peroxide-type free-radical initiator can be organic or inorganic, the organic having the general formula: Rxe2x80x2OORxe2x80x3 where Rxe2x80x2 is any organic radical and Rxe2x80x3 is selected from the group consisting of hydrogen and any organic radical. Both Rxe2x80x2 and Rxe2x80x3 can be organic radicals, preferably hydrocarbon, aroyl, and acyl radicals, carrying, if desired, substituents such as halogens, etc. Preferred peroxides include di-tert-butyl peroxide, tert-butyl peroxybenzoate, and dicumyl peroxide. Examples of other suitable peroxides, which in no way are limiting, include benzoyl peroxide; lauroyl peroxide; other tertiary butyl peroxides; 2,4-dichlorobenzoyl peroxide; tertiary butyl hydroperoxide; cumene hydroperoxide; diacetyl peroxide; acetyl hydroperoxide; diethylperoxycarbonate; tertiary butyl perbenzoate; and the like.
The azo-type compounds, typified by alpha,alphaxe2x80x2-azobisisobutyronitrile, are also well-known free-radical promoting materials. These azo compounds can be defined as those having present in the molecule the group xe2x80x94Nxe2x95x90N wherein the balances are satisfied by organic radicals, at least one of which is preferably attached to a tertiary carbon. Other suitable azo compounds include, but are not limited to, p-bromobenzenediazonium fluoroborate; p-tolyidiazoaminobenzene; p-bromobenzenediazonium hydroxide; azomethane and phenyldiazonium halides. A suitable list of azo-type compounds can be found in U.S. Pat. No. 2,551,813, incorporated herein by reference in its entirety.
The amount of initiator to employ, exclusive of radiation, depends to a large extent on the particular initiator chosen, the high reactivity olefin used and the reaction conditions. The usual concentrations of initiator are between 0.001 and 0.2 mole of initiator per mole of vinyl monomer reactant with preferred amounts between 0.005 and 0.10 mole of initiator per mole of vinyl monomer reactant.
Typically the reaction may be conducted at a temperature of about 30xc2x0 C. to about 350xc2x0 C., preferably from about 40xc2x0 C. to about 300xc2x0 C. However, the polymerization temperature must be sufficiently high to break down the initiator to produce the desired free-radicals. For example, using persulfate initiators, such as ammonium persulfate as the initiator, a polymerization temperature of at least about 40xc2x0 C., preferably about 40xc2x0 C. to about 120xc2x0 C., more preferably about 50xc2x0 C. to about 100xc2x0 C. and still more preferably, about 60xc2x0 C. to about 90xc2x0 C. can be used. Using benzoyl peroxide as the initiator, the reaction temperature can be between about 75xc2x0 C. and about 90xc2x0 C., preferably between about 80xc2x0 C. and about 85xc2x0 C. Higher and lower temperatures can be employed, a suitable broad range of temperatures being between about 20xc2x0 C. and about 200xc2x0 C., with preferred temperatures between about 50xc2x0 C. and about 150xc2x0 C.
The reaction pressure should be sufficient to maintain the solvent in the liquid phase. Pressures can therefore vary between about atmospheric and 100 psig or higher, but the preferred pressure is atmospheric. The reaction time is usually sufficient to result in the substantial conversion of the vinyl monomer reactant and high reactivity polyolefin to copolymer of the invention having the desired properties. The reaction time is generally between one and 24 hours, with preferred reaction times between two and ten hours.
The subject reaction can be an emulsion-type polymerization reaction, a solution-type polymerization reaction, a suspension-type polymerization reaction, a bulk-type polymerization reaction or a precipitation-type polymerization reaction. The high reactivity polyolefin, vinyl monomer reactant, solvent and initiator can be brought together in any suitable manner. The important factors are intimate contact of the high reactivity polyolefin and vinyl monomer reactant in the presence of a free-radical producing material.
For example, the components in the reaction mixture can be added continuously to a stirred reactor with continuous removal of a portion of the product to a recovery train or to other reactors in series. The reaction can also be conducted in a batch system where all of the high reactivity polyolefin is added initially to a mixture of vinyl monomer reactant, initiator and solvent, or the high reactivity polyolefin can be added intermittently or continuously to the reaction pot. Alternatively, the reactants may be combined in other orders; for example, vinyl monomer reactant and initiator may be added to high reactivity polyolefin and solvent in the reaction pot. The reaction can also suitably take place in a coil-type reactor where the components are added at one or more points along the coil.
In one envisioned embodiment, the reaction product of a vinyl monomer reactant and a high vinylidene-containing polyolefin is further reacted thermally. In this embodiment, any unreacted polyolefin, generally the more hindered olefins, i.e., the non-vinylidene polyolefins, that do not react readily with the vinyl monomer reactant under free radical conditions, are reacted with vinyl monomer reactant under thermal conditions, i.e., at temperatures of about 40xc2x0 C. to 300xc2x0 C.
The reaction solvent, as noted above, must be one which dissolves the initiator. Suitable solvents include water, liquid saturated or aromatic hydrocarbons having from six to twenty carbon atoms; ketones having from three to six carbon atoms; and liquid saturated aliphatic dihalogenated hydrocarbons having from one to five carbon atoms per molecule, preferably from one to three carbon atoms per molecule. By xe2x80x9cliquidxe2x80x9d is meant liquid under the conditions of polymerization. In the dihalogenated hydrocarbons, the halogens are preferably on adjacent carbon atoms. By xe2x80x9chalogenxe2x80x9d is meant fluorine, chlorine and bromine.
Examples of suitable solvents include, but are not limited to: water, ketones, such as acetone; methylethylketone; diethylketone; and methylisobutyl-ketone; aromatic hydrocarbons, such as benzene; xylene; and toluene; saturated dihalogenated hydrocarbons, such as: dichloromethane; dibromo-methane; 1-bromo-2-chloroethane; 1,1-dibromoethane; 1,1-dichloroethane; 1,2-dichloroethane; 1,3-dibromopropane; 1,2-dibromopropane; 1,2-dibromo-2-methylpropane; 1,2-dichloropropane; 1,1-dichloropropane; 1,3-dichloro-propane; 1-bromo-2-chloropropane; 1,2-dichlorobutane; 1,5-dibromopentane; and 1,5-dichloropentane; or mixtures of the above, such as benzene-methylethylketone.
If necessary, after the polymerization reaction has proceeded to the desired extent, the copolymer is conveniently separated from solvent and unreacted reactants by conventional procedures such as phase separation, solvent distillation, precipitation and the like. If desired, dispersing agents and/or cosolvents can be used during the reaction.
The resulting graft copolymers of the present invention can be used for the same applications as polymers and copolymers of the particular vinyl monomer or monomers used or the vinylidene monomer or monomers used. Such graft copolymers have improved impact strength and flexibility. For example, a copolymer of styrene and high reactivity polybutene having improved flexibility and impact resistance may find use in the same applications as currently available polystyrene. Use of free radical polymerization to incorporate polyolefins into vinyl and/or vinylidene polymers provides a means of imparting the beneficial qualities provided by the polyolefin by actually chemically incorporating it into the copolymer. It overcomes the problems associated with attempts to improve properties of vinyl polymers by physically incorporating polyolefins through mixing or blending. For example, when polybutene is physically blended into polystyrene, one can only get up to about 3% of polybutene into the polystyrene, and the result is just a physical mixture; the polybutene is not chemically incorporated into the polystyrene to form a copolymer as it is in the present invention. Furthermore, chemical incorporation of a given amount of the aforesaid highly reactive polyolefin into a polymer derived from the aforesaid vinyl and vinylidene monomer affords a greater improvement in the properties of the polymer derived from the vinyl or vinylidene monomer than does physical incorporation thereunto of even the same amount of the aforesaid highly reactive polyolefin.
The present invention also includes compositions containing a copolymer of the present invention and useful in coating, adhesive, paint, structural, film, sheet pipe, toy, house siding, asphalt, thermoplastic and elastomer applications. The present invention also includes a coating composition containing a copolymer of the present invention. The present invention is also a multilayer structure comprising at least one substrate coated with at least one layer of a coating comprising a copolymer of the present invention. The substrate may be any material capable of being coated with a copolymer of the invention or a coating composition containing a copolymer of the invention. Such substrates may include, but are not limited to metal, wood, concrete, plastic, paper, textiles, polymers, glass, fiberboard, composites, fibers porcelain, polymers films and sheets, and the like.
Some copolymers of the present invention, especially those made using acrylate or methacrylate monomers, have the advantage that they can be incorporated into coating formulations without the use of volatile organic compounds (VOCs). VOCs are not used or are reduced in the production of some compositions containing copolymers of the invention, for example, certain coatings, adhesives, paint formulations, and other products incorporating the copolymers. These compositions incorporating copolymers of the present invention are advantageous because they do not contain volatile organic compounds (VOCs). Since they can be made without using volatile organic compounds, costs are reduced as VOCs do not have to be purchased and disposed of, and any environmental problems, toxicity problems or special handling or disposal requirements associated with the use of VOCs are eliminated. Copolymers of the present invention may also have the advantages of demonstrating improved water absorption resistance, improved hardness characteristics, improved flexibility, and improved processability.
Thus, incorporating high reactivity polyolefins into polymers derived from vinyl and vinylidene monomers has many advantages, depending on the monomers chosen, including improving impact strength, melt flow, transparency, processing speed, chemical and water resistance, density, compatibility, flexibility, plasticization, toxicity, mildew resistance, environmental stress crack resistance (ESCR), and flexibility/strength.
For example, a copolymer of styrene-acrylonitrile (SAN), acrylonitrile-butadiene-styrene (ABS), or styrene-butadiene-rubber (SBR) with high reactivity polyisobutylene has improved impact strength, melt flow, processing speed, transparency, chemical resistance, density, and compatibility, and finds use in office equipment, automobile and other applications.
The acrylate and alkylacrylate copolymers of the present invention can be incorporated into water based coatings to improve water resistance and hardness characteristics. They can also be incorporated into paints and adhesives.
In general, the copolymers of the present invention find use in the same applications for which polymers of the vinyl and vinylidene monomers are used. Such applications are described in Concise Encyclopedia of Polymer Science and Engineering, Jacqueline I. Kroschwitz, Executive Editor, John Wiley and Sons, New York, 1990, incorporated herein by reference in its entirety; Encyclopedia of Polymer Science and Engineering, Second Edition, Editors Herman F. Mark, Norbert M. Bikales, Charles G. Overberger, George Menges, and Jacqueline I. Kroschwitz, John Wiley and Sons, New York, 1985, incorporated herein by reference in its entirety; Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition (1994) incorporated herein by reference in its entirety, and Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition (1994) incorporated herein by reference in its entirety.
A copolymer of polyvinyl chloride (PVC) with high reactivity polyisobutylene has improved flexibility; plasticization; impact resistance, density; melt flow; toxicity; and mildew resistance; and finds use in film applications, sheet applications, pipe applications, toy applications, structural applications; house/building siding applications; and internal lubricant applications. For example, dioctyl phthalate (DOP) which has toxicity problems, is used to add flexibility to polyvinyl chloride. Incorporating high reactivity polybutene or other high reactivity polyolefins into PVC using free radical polymerization provides copolymers which have improved flexibility without the use of DOP. Such copolymers find use in all the applications for which PVC is currently used. Such applications include, but are not limited to, those described in Concise Encyclopedia of Polymer Science and Engineering (1990) p. 1246-1254 incorporated herein by reference in its entirety. For example, PVC-containing copolymers of the present invention find use in pipe fittings, electrical and equipment housing, bottles, footwear, novelties, components, flooring, packaging sheet, film and foil, decorative laminates, thermoforming sheet, rigid sheet, sheet and foil swimming pool liners, waterproof membranes, toys, pipe: pressure, water, irrigation, drain/vent/waste, conduit, sewer/drain; profiles: GP profiles, window profile, composite windows, siding/cladding, drawer components, curtain rails; sheet and foils, foam sheet, pipe, and profile; hoses, tubes, film, cables, belting, waterstops and seals, and trim.
As another example, a copolymer of polystyrene with high reactivity polyisobutylene or another high reactivity polyolefin has improved impact resistance; environmental stress crack resistance (ESCR); chemical resistance; melt flow; transparency; density; and flexibility/strength; and finds use in asphalt applications; thermoplastic applications; and elastomer applications as well as in all the applications for which polystyrene is currently used. For example, copolymers of the present invention which incorporate styrene find use in packaging, appliances, construction, automotive parts, toys, housewares, luggage, medical ware, disposable food service, and electronic equipment. When fabricated using injection molding, such styrene copolymers find use in furniture, toys, radio and television cabinets, automotive parts, medical ware, housewares, bottle caps, containers, and the like. When fabricated using blow molding, such styrene copolymers find use in bottles, containers, furniture, automotive parts, and the like. When fabricated using extrusion, such styrene copolymers find use in film (including multilayer and oriented), profiles, light diffusers, wall covering, and the like. When fabricated using extrusion and thermoforming, such styrene copolymers find use in refrigerator and freezer parts, luggage, food containers (both solid and formed), disposable cups and dinnerware, large automotive parts, and the like. Foam applications include egg cartons, meat-packaging trays, building insulation, xe2x80x9cclamshellsxe2x80x9d for fast-food packaging, and expanded polystyrene cushioning materials for packaging. Applications for which styrene-derived copolymers of the present invention are used include, but are not limited to, those given for polystyrene in the section on xe2x80x9cStyrene Polymersxe2x80x9d in Concise Encyclopedia of Polymer Science and Engineering (1990) p. 1114-1140, incorporated herein by reference in its entirety.
Copolymers of high reactivity polyolefins and acrylonitrile-butadiene-styrene (ABS) find use in all the applications for which ABS is currently used. Applications for which ABS-derived copolymers of the present invention are used include those given for ABS in Concise Encyclopedia of Polymer Science and Engineering (1990) p. 25-27, incorporated herein by reference in its entirety. Such applications include, but are not limited to, use in appliances, in refrigerator doors, in tank liners, in automobiles and automotive applications, e.g., instrument panels, light consoles, pillar post moldings, and other interior trim parts, knobs, light bezels, mirror housings, decorative trim, and grills; use in building and construction, e.g., in pipe, fittings, and conduit. Other uses include use in business machines, telephones, consumer electronics, modifiers, luggage, packaging, and furniture.
Applications for which copolymers of the present invention derived from free radical polymerization of acrylic and methacrylic acids with high reactivity polyolefins are used include those given for acrylic and methacrylic acids and esters in the Encyclopedia of Polymer Science and Engineering, 2nd edition (1985) p. 221-231, incorporated herein by reference in its entirety. Such applications include, but are not limited to use as thickeners, e.g. for rubber, and other latexes, in petroleum recovery, in toothpaste, cosmetics, hydraulic fluids, and liquid rocket fuels; as ion-exchange resins; as suspending agents and dispersants, e.g., additives in drilling mud, pigment dispersants in paint or other colorant manufacture, with starch based paper-size formations, to improve the dispersion of cement in water and as cement additives; as flocculating agents, e.g. in treatment of potable and waste water, clarification of sugar cane juice, recovery of suspended metal ores in mining operations, clarification of used dry-cleaning fluids, in improving tilth and modifying water-holding capacity of clay soils; as binders, e.g., in ceramics, foundry core binder, and dental cements; as adhesives and in adhesive compositions; and in safety glass interlayers and in glass fiber plastic composites.
Applications for which copolymers of the present invention derived from free radical polymerization of acrylic and methacrylic esters with high reactivity polyolefins are used include, but are not limited to, those given for acrylic and methacrylic acids and esters in Encyclopedia of Polymer Science and Engineering, 2nd edition (1985) p.278-290, incorporated herein by reference in its entirety. Such uses include coatings, e.g. in paint formulations, surface finishes, e.g. prefinishing of wood, acrylic emulsions used in conjunction with nitrocellulose to provide clear industrial finishes, in aqueous latex-based maintenance paints; in textile finishing, e.g., as thickeners in the formulation of textile finishes; as temporary protective coatings applied to warp or single-end sizes; acrylic based emulsion polymers are used as permanent coatings for fabrics, to reduce shrinkage of wool, to improve abrasion resistance of textiles; to bond nonwoven fabrics, to bind pigments, as heat seal adhesives; and as a carpet-backing size; water-soluble acrylic based polymers are incorporated into carpet shampoo to impart soil retardancy; certain acrylic polymers find use as textile sizes, binders for glass fibers, in printing ink formulations for textiles; in textile backings, e.g., acrylic latex foams find use as backing for drapery or other fabric; as paper saturants and in paper coatings; as lubricating oil additives; for leather finishing and as acrylic polymer leather composites; as modifiers for cement impact strength and adhesion; as temporary binders, deflocculants, and additive components in ceramic bodies and glazes; as binders for aqueous and solvent-based caulks and sealants; in roof mastics; as processing aids and plate-out scavengers for both plasticized and unplasticized poly(vinyl chloride) in the manufacture of blown film and thin-gauge calendered film; in acrylic floor polishes; as coatings for plant leaves to help in controlling plant disease; in heat resistant seals; in glazing materials; in architectural applications such as domes over pools, archways, windows, as window mosaics, side glazing, patterned windows, color-coordinated structures and for solar control in sunscreens; biomedical applications include use in construction of custom appliances, dentures, teeth, denture bases and filling materials, as pit-and fissure resin sealants, high binder-strength dental and surgical bindings and filling agents, in bone cement, in contact lenses; in optical applications, such as light focusing plastic fibers, optical fibers, and lenses. Other applications include use in cultured marble plastic fixtures, thermoformed bathtubs, in toys, to improve water resistance of slate, in anion-exchange fibers and films; and opaque and clear methacrylate derived copolymer sheet find use in the construction of recreational vehicles.
Applications for which copolymers of the present invention derived from free radical polymerization of styrene and acrylonitrile with high reactivity polyolefins are used include, but are not limited to, those given for styrene-acrylonitrile (SAN) copolymers in Encyclopedia of Polymer Science and Engineering, 2nd edition (1985) p.452-464, incorporated herein by reference in its entirety. Such SAN derived copolymers find use in appliances, e.g., air-conditioner and other appliance parts, decorated escutcheons, washer and dryer instrument panels, washing-machine filter bowls, detergent dispensers, refrigerator shelves and crisper pans, blenders, mixers, lenses, knobs, and covers; in housewares, e.g., brush blocks and handles, broom and brush bristles, cocktail glasses, disposable dining utensils, hangers, ice buckets, jars, mugs, carafes, bowls, soap containers, tumblers, and food trays; in packaging materials, e.g. bottles, jars, vials, closures, containers, display boxes, and films; in automotive applications, e.g., batteries, bezels, lenses, signals, dash components, and interior trim; in industrial applications; e.g., batteries, transmitter caps, business machines, instrument covers, tape and data reels, medical apparatus and equipment such as syringes, blood aspirators, petri dishes, cell culture bottles, artificial kidney devices; in custom molding products, e.g., aerosol nozzles, bottle sprayers, camera parts, dentures, pen and pencil barrels, sporting goods, toys, telephone parts, filter bowls, tape dispensers, and terminal boxes; in concrete composites; and in electrical/electronics components.
Applications for which copolymers of the present invention derived from free radical polymerization of a vinyl ester such as vinyl acetate and at least one aforesaid vinyl monomer with a high reactivity polyolefin are used include, but are not limited to, those given for vinyl ester polymers in Encyclopedia of Polymer Science and Engineering, 2nd edition (1985) p.406-422, incorporated herein by reference in its entirety. Such uses include use in adhesives and adhesive films such as emulsion films and plasticized films; in coatings and paints; in paper and paperboard coatings; in textile finishes; in binding agents for nonwoven fabrics; as antishrink agents for glass-fiber-reinforced polyester molding resins; as binders for fibers, leather, asbestos, sawdust, sand, clay, and other materials to form compositions that can be shaped with heat and pressure; in concrete, joint cements, taping compounds, caulks and fillers; in light-sensitive stencil screens for textile printing and ceramic decoration; in printing inks, lacquers, and high gloss coatings; as chewing-gum bases; in controlled release agents for administration of drugs and other chemicals; and as a base for antifouling marine paints.
The present invention also includes a copolymer of (a) at least one vinyl monomer of the formula CH2xe2x95x90C(R)OC(O)R3 where R3 is C1-C4 alkyl; (b) at least one vinyl monomer having the formula CH2xe2x95x90C(R)X where R is hydrogen or C1-C6 alkyl, and X is halogen, phenyl or phenyl substituted with C1-C4 alkyl, xe2x80x94COOR1 where R1 is hydrogen or C1-C12 alkyl, xe2x80x94Cxe2x89xa1N, xe2x80x94C(O)NR2R3 where R2 and R3 are hydrogen or C1-C4 alkyl and may be the same or different, xe2x80x94(CH2)nCOOR1 where R1 is hydrogen or C1-C12 alkyl and n is an integer of from 1 to 4, or xe2x80x94CHxe2x95x90CHZ where Z is hydrogen or C1-C8 alkyl; or where both R and X are halogen, and (c) at least one high reactivity polyolefin having a terminal vinylidene content of at least about 40% and a number average molecular weight of about 200 to about 10,000. Preferably, the vinyl monomer of the formula CH2xe2x95x90C(R)OC(O)R3 is vinyl acetate. Preferably, the vinyl monomer of the formula CH2xe2x95x90C(R)X is a compound of the formula: CH2xe2x95x90CHX where X is chlorine, phenyl, or phenyl substituted with C1-C4 alkyl; CH2xe2x95x90C(R)COOR1 where R is hydrogen or C1-C4 alkyl and R1 is hydrogen or C1-C10 alkyl; CH2xe2x95x90CHCxe2x89xa1N; CH2xe2x95x90CHC(O)NR2R3 where R2 and R3 are hydrogen or C1-C4 alkyl and may be the same or different; CH2xe2x95x90C(R)(CH2)nCOOR1 where R is hydrogen or C1-C4 alkyl, R1 is hydrogen or C1-C10 alkyl and n is an integer of from 1 to 4; or CH2xe2x95x90CHxe2x80x94CHxe2x95x90CHZ where Z is hydrogen or C1-C4 alkyl. In an alternative preferred embodiment, the vinyl monomer of the formula CH2xe2x95x90C(R)X is a compound of the formula: CH2xe2x95x90C(R)X where R is hydrogen or C1-C4 alkyl and X is phenyl or phenyl substituted with C1-C4 alkyl; CH2xe2x95x90C(R)COOR1 where R is hydrogen or C1-C4 alkyl and R1 is hydrogen or C1-C10 alkyl; CH2xe2x95x90CHCxe2x89xa1N; CH2xe2x95x90CHC(O)NR2R3 where R2 and R3 are each hydrogen or C1-C4 alkyl and may be the same or different; CH2xe2x95x90CHR4 where R4 is halogen, preferably chlorine; CH2xe2x95x90C(R)(CH2)nCOOR1 where R is hydrogen or C1-C4 alkyl, R1 is hydrogen or C1-C10 alkyl and n is an integer of from 1 to 4; or CH2xe2x95x90CY2 where Y is fluorine or chlorine.
Polyvinyl acetate-containing copolymers of the present invention are converted to poly(vinyl alcohol)-containing copolymers by hydrolysis or catalyzed alcoholysis. Applications for such copolymers of vinyl alcohols and high reactivity polyolefins of the present invention include, but are not limited to, those given for vinyl alcohol polymers in Encyclopedia of Polymer Science and Engineering, 2nd edition (1985) p.183-193, incorporated herein by reference in its entirety. Such uses include use in textiles and warp sizing, in adhesives, polymerization stabilizers, in building products, e.g., in cement coatings and finishes, dry-wall joint cements, stucco finishes, thin bed tile mortars, cement paint, roof coatings and cement toppings for repairs; as fibers, films, protective coatings, e.g., for metals, plastics, and ceramics, in photoengraving, photogravure, screen printing, printed-circuit manufacture, and color television tube manufacture; in cosmetic applications; as a viscosity builder for aqueous solutions or dispersions, and in paper and paperboard coatings.
Polyvinyl alcohol-containing copolymers of the present invention can be converted to poly(vinyl acetal)xe2x80x94containing copolymers of the present invention by condensation with an aldehyde in the presence of an acid catalyst. Poly(vinyl butyral)-containing copolymers of the invention find use in applications for which poly(vinyl butyral) is used, for example, as an interlayer in automotive and aircraft safety glazings, in safety glass. Lower poly(vinyl acetal)-containing copolymers of the present invention such as those containing poly(vinyl formal) find use in enamels for coating electrical wire and in self-sealing gasoline tanks.